Halogen containing phosphorus monools

ABSTRACT

Novel halohydrocarbyl mono hydroxy containing phosphites and phosphonates are prepared. They can be converted to fire resistant polyurethanes or used as stabilizers and fire retardant additives in various compositions.

United States Patent [1 1 Boyer Sept. 11, 1973 HALOGEN CONTAINING PHOSPHORUS [56] References Cited MONOOLS UNITED STATES PATENTS [75] Inventor: Nicodemus E. Boyer, Parkersburg, 3,333,028 7/1967 Larrison 260/953 X W. Va. 3,463,837 8/1969 Friedman 260/953 X [73] Assignee: mug-Warner Corporation, Chicago, Primary Examiner Lewis Gotts Assistant ExaminerAnton H. Sutto [22] Filed: July 16, 1970 Attorney-Cushman, Darby & Cushman [21] Appl. No.: 55,575

[57] ABSTRACT Novel halohydrocarbyl mono hydroxy containing phos- [52] ig gggb f g phites and phosphonates are prepared. They can be 260/942 5 converted to fire resistant polyurethanes or used as sta- Int Cl C07 9/08 6, 9/40 6 g 22). bilizers and fire retardant additives in various composi- [58] Field of Search 260/953, 950

36 Claims, N0 Drawings IIALOGEN CONTAINING PHOSPIIORUS MONOOLS The present invention relates to novel organic phosphites and phosphonates.

The organic phosphites and phosphonates of the present invention are all characterized by having a single hydroxyl group. This hydroxyl group is not on a carbon atom adjacent to a phosphorus atom and is normally linked to the phosphorus atom through a plurality of atoms terminating in an oxygen atom which is directly attached to the phosphorus atom. The phosphites and phosphonates are further characterized by having at least one halogen atom of atomic weight not over 80 attached to a carbon atom attached either directly or indirectly to a phosphorus atom. Preferably the compounds have a plurality of such halogen atoms.

The compounds of the present invention are useful in preparing flame resistant and fire retardant polyesters and polyurethanes. They take part in the reaction forming the polyester or polyurethane and surprisingly even though they are monofunctional, i.e. they have only one hydroxyl group. They do not interfere with the reaction of poly-functional alcohols in reacting with polybasic acids to form polyesters or in reacting with polyisocyanates to form polyurethanes. On the other hand because they take part in the reaction they are permanently bound in the product and cannot be leached out or otherwise removed in the manner that non-reactive halogenated phosphites or phosphonates can be removed.

bromide, octyl fluoride, octyl chloride, octyl bromide, l,2-dichloropropane, 1,2-dibromopropane, 1,3- dichloropropane, 1,4-dichlorobutane. These halogen compounds can be added in either catalytic amounts, e.g. 0.1 mole per mole of bis(alkyl) diol phosphite (or bis(haloalkyl) diol phosphite) or they can be used in equimolar amounts. In the rearrangement, the haloalkane will react to replace a part of the alkyl or haloalkyl groups, depending on the amount of haloalkane and phites having a single hydroxyl group such as bis(2- The novel phosphites and phosphonates also can be used in other formulations, e.g. in amounts 0.1-10 percent by weight of the polymer as stabilizers against oxidation, light and other polymer degradation for polyvinyl chloride, and other vinyl chloride polymers, e.g. vinyl chloride-vinylidene chloride copolymer (80:20), vinyl chloride-vinyl acetate (87:13), vinyl chlorideacrylonitrile (85:15). In the same proportions they are also stabilizers for monoolefin polymers such as polyethylene, polypropylene, ethylene-propylene copolymers (e.g. 50:50, 80:20 and 20:80), ethylene-monoolefin copolymers wherein the monoolefin has four to 10 carbon atoms and is present in a minor amount, e.g. ethylene-butene-l copolymer (e.g. 95:5) and ethylenedecene-l copolymer. Furthermore, they can be used in the same amounts to stabilize natural rubber, styrenebutadiene rubber, ethylene-propylene-nonconjugated diene terpolymers, e.g. ethylene-propylenedicyclopentadiene terpolymer (e.g. 57:42:13), poly cis isoprene, poly cis butadiene, as well as ABS (acrylonitrile-butadiene-styrene) polymer.

The various types of phosphites and phosphonates which are suitable for use in the invention will be discussed in more detail below.

Unless otherwise indicated, all parts and percentages are by weight.

It should be realized that almost all of the compounds of the present invention exist as a mixture of several In the Arbuzov rearrangement of phosphites to phosphonates there can be used any desired haloalkane such as ethylene dichloride, 2-chloroethanol, chloroform, bromoform, carbon tetrachloride, carbon tetrachloroethyl) hydroxyethyl phosphite, bis (2- chloroethyl) hydroxypropyl phosphite, bis(2- chlor'oethyl) 4-hydroxybutyl phosphite, bis(2-chloroethyl)2-hydroxybutyl phosphite, bis(2-chloroethyl) hydroxyethoxyethyl phosphite, bis(Z-chloro-ethyl) hydroxypropoxypropyl phosphite, bis(Z-chloroethyl) hydroxy di(ethoxy) ethyl phosphite, bis(Z-chloroethyl) hydroxy di(propoxy) propyl phosphite, bis(2- chloroethyl) hydroxy tri(ethoxy) ethyl phosphite, bis(2-chloroethyl) hydroxy tri(propoxy) propyl phosphite, bis(2-bromoethyl) hydroxy di(ethoxy) ethyl phosphite, bis(2,3-dichloropropyl) hydroxyethyl phosphite, bis(2,3-dibromopropyl) hydroxypropoxypropyl phosphite, bis(2-chloroethyl) hydroxyhexyl phosphite. In the reaction hydrogen chloride is-eliminated in the form of a salt, e.g. as tertiary amine hydrochloride such as triethylamine hydrochloride. An alternative method for preparing compounds of the above type is to react tris(haloalkyl) phosphites with an equimolar amount of the diol and remove 1 mole of chlorohydrin, e.g. by distillation. The reaction can be carried out in the presence of alkali as a catalyst, e.g. 0.1 mole of sodium methylate. The compounds formed have the formula where Y N is a tertiary amine. Alternatively the compounds can be formed by the reaction Examples of such compounds are bis(chlorophenyl) hydroxyethyl phosphite, bis(pentachlorophenyl) diethylene glycol phosphite, bis(2,3-dibromophenyl) dipropylene glycol phosphite, bis(2,4-dichloronaphthyl) hydroxypropyl phosphite.

Phosphonates analogous to the above phosphites can be prepared by a conventional Arbuzov rearrangement of the phosphite by heating in the presence of an alkyl halide (it being remembered that the haloaryl groups will not undergo the Arbuzov rearrangement).

Thus there can be formed 2-chloroethyl hydroxyethyl 2-chloroethane phosphonate, 2-chloroethyl hydroxypropyl 2-chloroethane phosphonate, 2- chloroethyl 4'-hydroxybutyl 2-chloroethane phosphonate, 2-chloroethyl 2-hydroxybutyl 2-chloroethane phosphonate, 2-chloroethyl hydroxyethoxyethyl 2- chloroethane phosphonate, 2-chloroethyl hydroxypropoxypropyl 2-chloroethane phosphonate, 2- chloroethyl hydroxydi-(ethoxy)ethyl 2-chloroethane phosphonate, 2-chloroethyl hydroxydi- (propoxy)propyl 2-chloroethane phosphonate, 2- chloroethyl hydroxy tri(ethoxy)ethyl 2-chloroethane phosphonate, 2-chloroethyl hydroxytri(propoxy)propyl 2-chloroethane phosphonate, 2-bromoethyl hydroxydi(ethoxy)ethyl 2-bromoethane phosphonate, 2,3-dichloropropyl hydroxyethyl 2,3-dichloropropane phosphonate, 2,3-dibromopropyl hydroxypropoxypropyl 2,3-dibromopropane phosphonate, 2-chloroethyl hydroxyhexyl 2-chloroethanephosphonate.

By reacting one mole chloroethyl phosphorodichloridite with 2 moles of propylene oxide there is formed 2- chloroethyl.bis(2-chloropropyl) phosphite. Transesterification of this with diols, e.g. diethylene glycol, dipropylene glycol, tripropylene glycol or the other diols set forth above by heating below 100 C. forms ethylene chlorohydrin as the by-product and bis(2- chloropropyl) hydroxyethoxyethyl phosphite, bis(2- chloropropyl) hydroxypropoxypropyl phosphite, bis(2- chloropropyl) hydroxydi(propoxypropyl) phosphite, bis(2-chloropropyl) hydroxybutyl phosphite, bis(2- chloropropyl) hydroxypropyl phosphite. Similar bromine analogues are formed starting from 2- boromoethyl phosphorodibromidite, e.g. bis(2- bromopropyl) hydroxyethoxyethyl phosphitej These compounds upon heating to 100-150C. rearrange into the corresponding phosphonates by Arbuzov rearrangement to form 2-chloropropyl hydroxypropoxypropyl 2-chloropr0pane phosphonate, 2-chloropropyl hydroxyethoxyethyl 2-chloropropane phosphonate, 2- chloropropyl 2-hydroxybutyl 2-chloropropane phosphonate, 2-bromopropyl hydroxyethoxyethyl 2- bromopropane phosphonate (as well as isomers).

EXAMPLE 1 Bis(2-chloroethyl) hydroxyethoxyethyl phosphite.

One mole (225.5 gr.) of bis(2-chloroethyl) phosphorochloridite (made from 1 mole of phosphorus trichloride and 2 moles of ethylene oxide at 3540C. in hours) was reacted with 1 mole (106.1 g.) of diethylene glycol and 1 mole (101 g.) of triethylamine in 1 liter of diethyl ether to form 1 mole of triethylamine hydrochloride which was filtered off and 1 mole of bis(2- chloroethyl hydroxyethoxyethyl .phosphite ((CICH C- H,0),P-OCH CH,OCH,CH OH) as a colorless liquid in percent yield (C 32.72%, H 5.93%, Cl 24.00%, P 10.38%).

EXAMPLE2 Bis(2-chloroethyl) hydroxyethoxyethyl phosphite.

530.6 grams (5 moles) of diethylene glycol were EXAMPLE 3 Bis(2-chloroethyl) hydroxypropoxypropyl phosphite. 670.9 grams (5 moles) of dipropylene glycol were placed in a flask under a nitrogen atmosphere. The dipropylene glycol was heated to C. and 1347.5 grams (5 moles) of tris(2-chloroethyl) phosphite added gradually. The temperature dropped to 1 12C. and was kept at 102l 12C. for about 1.5 hours while removing the 2-ch1oroethanol formed by distillation. The residue in an amount of 1576.8 grams was bis(2- chloroethyl) hydroxypropoxypropyl phosphite, a clear very pale yellow liquid, C 37.54%, H 6.94%, P 8.87%, Cl 20.30%; d 1.160. The iodine number of 69.55 to 69.30 as against a theoretical of 78.5 shows that there was little rearrangement to the corresponding phosphonate. The iodine number is calculated as (l /Mo]. Wt.) X 100 iodine number since the reaction is I 2.5 moles of bis(2-chloroethyl) hydroxyethoxyethyl phosphite with 2.5 moles of carbon tetrachloride were refluxed for about 9.5 hours at 85C. residue temperature. Then volatiles were removed for 0.5 hours-at 760 mm. and a vapor temperature of 71C. and then for about 0.75 hours at a vapor temperature of 38C. and pressure of 69mm. to a vapor temperature'of 59C.

and pressure of 23 mm. The residue was a mixture of 2-chloroethyl hydroxyethoxyethyl trichloromethane phosphonate with some 2-chloroethyl hydroxyethoxyethyl 2-chlor'oethane phosphonate, unreacted bis(2- chloroethyl) hydroxyethoxyethyl phosphite and some dimer formed by splitting out 2-chloroethanol. The product was useful in making fire'retardant polyurethane foams.

EXAMPLE 5 2.5 moles of bis(2-chloroethyl) hydroxyethoxyethyl phosphite and 2.5 moles of ethylene dichloride were refluxed for 9.5 hours at about 103C. residue temperature. Then the volatiles were distilled off. There were collected 240.3 grams distilling at 8894C. at 760 mm. and 101.9 grams distilling at 44C. and 85 mm. to 67C. and 49 mm. The residue was 2-chloroethyl hydroxyethoxyethyl 2-chloroethane phosphonate as a nearly clear colorless liquid 11, 1.315 iodine number 56.32 to 56.26 indicating that there was present some unreacted bis(2-chloroethyl) hydroxyethoxyethyl phosphite as well. The yield was 593.3 grams. The completeness of the rearrangement is denoted by the decrease in iodine number from that of the starting phosphite. In other runs at a higher temperature, a complete rearrangement to the phosphonate (with the iodine number zero) was obtained.

EXAMPLE 6 2.322 moles of bis(2-chloroethyl) hydroxypropoxypropyl phosphite was refluxed with 1.161 moles of carbon tetrachloride for about 9.5 hours at about 112C. residue temperature. The volatiles were distilled first at atmospheric pressure at 7080C. and then at reduced pressure ending at 62C. and 39 mm.'The residue of 677.0 grams was a nearly clear, colorless liquid comprising primarily a mixture of about equal parts of 2- chloroethyl hydroxypropoxypropyl trichloromethane phosphonate and 2-ch1oroethyl hydroxypropoxypropyl 2-chloroethane phosphonate together with some unreacted starting phosphite and some dimer. The dimer was formed by the reaction (ClCHgCHzO)gPOCHCH OCHZCHQ P-O CH2CH2C1 H: CH3 'OCHCHzOCHIOHOH H Ha I ClCHzCHzOI-I The iodine number of 26.35 to 26.84 shows that there was substantial rearrangement to the phosphonates since the starting phosphite material employed had an iodine number of 69.30 to 69 .55.

EXAMPLE 7 2.322 moles of bis(2-chloroethyl) hydroxypropoxypropyl phosphite were refluxed with 2.322 moles of ethylene dichloride for 9.5 hours at a residue temperature of about 1 10C. The volatiles were distilled first at hydroxypropoxypropyl phosphite as a clear, colorless liquid, iodine number 66.29, C 37.12%, H 6.42%, P 9.35%, Cl 21.92%.

EXAMPLE 9 EXAMPLE l0 Bis(2,3-dichloropropyl) phosphorochloridite was prepared by adding 1.178 moles of epichlorohydrin to 0.589 mole of PCI; (i.e. a mole ratio of 2:1) during 1 hour at 25-50C. followed by heating the mixture for 1 hour at 70C. (C 22.8%, H 3.17%, CI 52.94%, P 9.06%). Then 79.0 grams (0.589 mole) of dipropylene glycol was added to the bis(2,3-dich1oropropyl) phosphorochloridite under the nitrogen during 1 hour and 23 minutes at 6679C. Heating was continued at 70-75C. for 1 additional hour and then for 2 hours at 130-135C. The pressure was reduced to 2124 mm. and the mixture heated further. The distillate coming over at 103105C. was primarily 2,3- dichloro'propanol. The liquid residue was primarily 2,3- diehloropropanol. The liquid residue was primarily bis(2,3-dichloropropy1) 6-hydroxy-4-oxahept-2-y1 phosphite in an amount of 169.6 grams, iodine number 67.4; C 32.75%, H 5.57%, C137.52%, P 9.29%.

EXAMPLE 1 1 287.1 grams (0.692 mole) of tris(2,3- dichloropropyl) phosphite were mixed with 92.9 grams (0.692 mole) of dipropylene glycol at 25C. and then Y heated for 0.5 hour to 122C. under nitrogen. The 2,3-

86 to 91C. at 760 mm. and then in a vacuum at a tem- EXAMPLE 8 Example 3 was repeated using 10 moles of tris(2- chloroethyl) phosphite and 10 moles of dipropylene glycol to obtain 3,209.4 grams of bis(Z-chloroethyl) dichloropropanol formed was removed by distillation at 10,8-1 17C. at 71-72.5 mm. In all 96.7 grams of.dis-

tillate were removed during 1 hour and minutes.

EXAMPLE 12 116 grams (0.283 mole) of the bis(2,3- dichloropropyl) hydroxypropoxypropyl phosphite prepared in Example 11 was heated at 150C. for 11.5 hours. The 2,3-dichloropropyl hydroxypropoxypropyl 2,3-dichloropropane phosphonate formed was recovered'as a clear, nearly colorless liquid in an amount of grams, iodine number 7.65, C 33.48%, H 5.20%, C1 35.39%, P 6.50%. The drop in iodine number as compared to that of the product of Example 11 indicated the increase in rearrangement to the phosphonate.

EXAMPLE13 1160.0 grams (0.283 mole) of bis(2,3-

dichloropropyl) hydroxypropoxypropyl phosphite having an iodine number of 30.68 and prepared in Example l l were mixed with 3.2 grams of ethylene chloride and refluxed for about 18.75 hours at 150C. The ethylene chloride was distilled off to leave as the residue 2,3- dichloropropyl hydroxy propoxypropyl 2,3- dichloropropane phosphonate, a nearly clear, colorless liquid in a yeild of 103.8 grams, iodine number 6.10, C 35.81%, H 5.59%, Cl 34.95%, P 7.45%.

EXAMPLE 14 The procedure of Example 3 was repeated by mixing 918.0 grams (3.405 moles) of tris(2-chloroethyl) phosphite with 457.0 grams (3.405 moles) of dipropylene glycol at 25C. and then heating to distill out the 2- chloroethanol formed at the water pump at a residue temperature up to 108C. at 33 to 18 mm. to obtain 278.6 grams of 2-chloroethanol. The residue was bis(2- chloroethyl) hydroxypropoxypropyl phosphite, a very pale yellow liquid weighing 1,073.7 grams, iodine number 73.62, C 37.53%, H 6.63%, P 8.81%, Cl 22.28%.

EXAMPLE 15 999.0 grams (3.705 moles) of tris(2-chloroethyl) phosphite and 393.2 grams (3.705 moles) of diethylene glycol were mixed at 75C. in a nitrogen atmosphere and then heated. The 2-chloroethanol formed was removed by distillation up to 115C. residue temperature using water pump vacuum. 313.4 grams of distillate were removed. The bis(2 -chloroethyl) hydroxyethoxyethyl phosphite residue in an amount of 1054.8 grams was clear and colorless, had an iodine number of 80.27 (theory86) and analyzed C 33.79%, H 6.19%, P 9.98%, CI 22.50

EXAMPLE 16 EXAMPLE17 455.1 grams (1.097 moles) of tris(2,3- dichloropropyl) phosphite were mixed with 116.5 grams (1.097 moles) of diethylene glycol at 25C. and heated up to l 19C. residue temperature while distilling off the 2,3-dichloro-l-propanol formed at 72 to 84C. at 27 to 22 mm. The distillate, was 101.8 grams (about 72% of theory). The residue was a clear, colorless liquid-containing 459.0 grams and was bis(2,3- dichloropropyl) hydroxyethoxyethyl phosphite mixed with some starting tris(23-dichloropropyl) phosphite. It had an iodine nmber of 55.27 (theory 64.7) and C 31.23% H 5.02%, Cl 37.50% P 7.25%.

EXAMPLE 18 2,746.8 grams (8.5 moles) of bis(2-chloroethyl hydroxypropoxypropyl phosphite were heated with 84.1 grams (.85mole of ethylene dichloride in a nitrogen atmosphere for 1.75 hours at reflux 145-150C. The product at this point had an iodine number of 29 showing partial transformation to 2-chloroethyl hydroxypropoxypropyl 2-chloroethane phosphonate. The product was then refluxed for 6.25 hours. at 760 mm. The residue was 2-chloroethyl hydroxypropoxypropyl 2-chloroethane phosphonate, iodine number 16.29, C 37.84%, H 6.69%, P 8.97%, Cl 20.72%.

EXAMPLE 19 2,804.0 grams (9.5 moles) of bis(2-chloroethyl) hydroxyethoxyethyl phosphite were mixed with 94.0

grams (0.95 mole) of ethylene dichloride at 25C. and heated to reflux under nitrogen at 140-150C. for 9 hours. The iodine number was 16.40 indicating substantial rearrangement to 2-chloroethyl hydroxyethoxyethyl 2-chloroethane phosphonate. The product was refluxed a further 7 hours'at 140C. Then the ethylene dichloride was distilled off at 760 mm. to give 101.8 grams of distillate. The residue. was a nearly clear, colorless slightly viscous liquid in an amount of 2,777.2

grams, iodine number l3.29,'C 32.54%, H.5.86%, P

10.69%, Cl'25.35% which indicated that most of the phosphite had rearranged to the phosphonate.

EXAMPLE 20 Bis(2-ch1oroethyl) hydroxypropoxypropyl phosphite was prepared by mixing 3,233.9 grams (12 moles) of tris (2-chloroethyl) phosphite with 1,610.0 grams ('12 moles) of dipropylene glycol. The mixture was heated to a pot temperature of -85C. at 49-32 mm. while distilling off the 2-chloroethanol by-product for 3 hours at which time 979.5 grams of distillate collected. The residue was a clear, light yellow liquid weighing 3,884.0 grams, Cl 21.91%, (theory 21.94), iodine number 71.9 (theory 78.5).

EXAMPLE 2 Bis(2-ch1oroethyl) hydroxyethoxyethyl phosphite was preparedby mixing 3,773.0 grams (14.0 moles) of tris (2-chloroethyl) phosphite and 1,486.8 grams (14.0 moles) of diethylene glycol and distilling off the 2 chloroethanol by-product for 3.5 hours at 23 mm. and 6583C. The distillate weighed 1140 grams. The residue was a clear, pale yellowish liquid weighing 4,109.8 grams, Cl 23.47%, iodine number 76.34 (theory 86.0).

EXAMPLE 22 A 2-chloroethyl hydroxyethoxyethyl trichloromethane phosphonate mixture like, that obtained in Example 4 was obtained by heating 914.8 grams (3.1 moles) of tris(2-chloroethyl) phosphite with 476.8 grams (3.1 moles) of carbon tetrachloride under nitrogen ata reflux temperature of C. for 8 hours and then distilling out 391.2 grams of volatiles (carbon tetrachloride and ethylene dichloride) at 870 mm. and 66 to 86C. (vapor) and up to a 153C. residue temperature in 2 hours. The residue contained 991.2 grams and had an iodine number of 12.9 indicating that most of the starting.

phosphite had been transformed to phosphonate.

EXAMPLE 23 560.83 grams (1.8 moles) of tris(2-chloropropyl) phosphite were mixed with 191.16 grams (1.8 moles) of diethylene glycol at 25C. and heated under nitrogen at the water pump to distill off the 2chloro-l-propanol by-product as it formed. It was heated for 1.5 hours up to 78C. residue temperature. The distillate (vapor) temperature was 50-62C. at 23-61 mm. and the distillate amounted to 181.9 grams. The residue was bis(2- chloropropyl) hydroxyethoxyethyl phosphite, a clear, colorless, slightly viscous liquid obtained in an amount of 562.1 grams, iodine number 75.73 (theory 78.5), C 37.01%, H 6.71%, Cl 21.28%, P 9.75%.

EXAMPLE 24 275.0 grams (0.851 mole) of bis(2-chloropropyl) hydroxyethoxyethyl phosphite and 8.4 grams (0.0851 mole) of ethylene dichloride were mixed and heated under nitrogen to reflux at 160-l65C. for 12.5 hours. Then the ethylene dichloride and the 1,2- dichloropropane formed were distilled off at up to 77C. residue temperature. The 2-chloropropyl hydroxyethoxyethyl 2-chloropropane phosphonate was obtained as a clear, colorless liquid in an amount of 255.9 grams, iodine number 14.63, C -34;9l%, H 6.15%, CI 27.34%, P 10.29%.

EXAMPLE 25 Bis(2-chloropropyl) hydroxypropoxypropyl phosphite was prepared by heatingequimolar amounts of tris(2-chloropropyl) phosphite and dipropylene glycol and distilling off the 2-chloro-1-propanol formed in a manner analogous to Example 23. To 310.0 grams (0.883 mole) of bis(Z-chloropropyl) hydroxypropoxypropyl phosphite there were added 8.7 grams (0.883 mole) of ethylene dichloride-and the mixture heated under reflux in a nitrogen atmosphere at slow reflux for 13 hours at 155-1 60C. The ethylene dichloride (and the 1,2-dichloropropane formed) were removed by distillation up to 160C. The residue was 2-chloropropyl hydroxypropoxypropyl 2-chloropropane phosphonate, a nearly clear colorless liquid obtained in a yield of 292.9 grams, iodine number 12.64 (theory zero), C 40.37%, H 7.23%, Cl 19.94k P 8.76%.

EXAMPLE 26 140.0 grams (0.433 mole) of bis( 2-chloropropy1) hydroxyethoxyethyl phosphite was mixed with 6.7 grams (0.043 mole) of carbon tetrachloride and heated to 150C. under nitrogen at reflux for 13.5 hours. Then the residual CCl, and 1,2-dichloropropane formed were removed by distillation. The residual product was a nearly clear, colorless slightly viscous liquid weighing 136.8 grams having an iodine number of 17.90; It was a mixture of about mole per cent 2-chloropropyl hydroxy ethoxyethyl trichloromethane phosphonate and about 90 mole'per cent of 2-chloropropyl hydroxyethoxyethyl 2-chloropropane phosphonate (based on total phosphonate). There was also a small amount of residual starting material. The analysis was C 34.88%, H 6.07%, Cl 22.14%, P 10.31%.

EXAMPLE 27 fluxed in a nitrogen atmosphere at 150C. for 12 hours. Residual CCl, and 1,2-dichloropropane formed were removed by distillation. The product was mainly 2- chloropropyl hydroxypropoxypropyl 2-chloropropane phosphonate with a small amount (not over 10 percent) 2-chloropropylhydroxypropoxypropyl trichloromethane phosphonate and a small amount of starting phosphite; iodinenumber 12.24, C 39.61%, H 6.90%,-

EXAMPLE 2:;

268.3 grams 2.0 moles) of dipropylene glycol were mixed with 1 liter of diethyl ether (solvent) and 202.0 grams (2.0 moles) of triethylamine (acid aceptor) at 25C. Then 450.9 grams (2.0 mole of bis(2- chloroethyl) phosphorochloridite in 350 ml. of diethyl ether were added dropwise during 2 hours at 2530C. while maintaining the mixture in a nitrogen atmosphere. The white precipitate of triethylamine hydrochloride was removed by filtration. The filtrate was concentrated on a flash evaporator to remove the ether to obtain bis(2-chloroethyl) hydroxypropoxypropyl phosphite as a colorless liquid in an amount of 666.7 grams, iodine number 62.10 (theory 78.6), C 38.84%, H 7.18%, Cl 21.06%, P 7.98%.

EXAMPLE 29 3,772.9 grams (14 moles) of tris (2-chloroethyl) phosphite and 1,485.7 grams (14 moles) of diethylene glycol were mixed at 25C. and then heated as set forth in Example 21 but at a pot temperature of 8090C. using a water pump pressure of 65-45 mm. 1,172.0 grams of 2-chloroethanol, distillate was formed. The yield of bis(2-chloroethyl) hydroxyethoxyethyl phosphite was 4,045.4 grams, Cl 22.57%, iodine number 81.04.

EXAMPLE 30 1829.6 grams (6.2 moles) of bis(2-chloroethyl) hydroxyethoxyethyl phosphite and 953.6 grams (6.2 moles) of carbon tetrachloridewere mixed and refluxed at 95C. for 5.75- hours to an iodine number of 16.17. The mixture was then refluxed for a further 7 hours at 95C. and then distilled at 760 mm. up to 153C. residue temperature in 3 hours. The distillate came over at 72 82C., mostly at about 76C. and amounted to 777.5 grams. The residue was nearly clear, colorless, slightly viscous liquid weighing 1,897.8 grams and having an iodine number of 3.64,-was a mixture of primarily 2-chloroethy1 hydroxyethoxyethyl tric'hloromethane phosphonate with some 2-chloroethyl hydroxyethoxyethyh2 ch1oroethane 'phosphonate and some phosphonate dimer. C 29.54%, H 4.93%, Cl 29.14%, P10.76%.,

. EXAMPLE 31 2,262.1 grams (7.0 moles) of bis(2-chloroethyl) hydroxypropoxypropyl phosphite and 1,076.6 grams (7.0 moles) of CCl, were heated under nitrogen at C. reflux for 4 hours to an iodine number of 14.22. Reflux was continued for another 7 hours at about 95-100C. and then distillate was removed at 760 mm. at up to 152C.residue temperature. About 732.2 grams of distillate were obtained in 4 hours. The residue was a nearly clear, colorless, slightly viscous liquid weighing 2,334.2 grams, iodine number 6.43. It was a mixture of primarily 2-chloroethyl hydroxypropoxy- 11 propyl trichloromethane phosphonate with some 2- chloroethyl hydroxypropoxypropyl 2-chloroethane phosphonate and some phosphonate dimer.

Example 32 ClCHaCHaO POCH1CiJHCHrOP OCHsCHnCl ClCHiCHzO OCHzCHqCl ZOICHQCHQOH or the isomeric ClCHaCI-IaO P-OCH2$HCH2OH ClCHzCHzO (I) In a similar way there can be prepared tetra (2- bromoethyl 2-hydroxypropylene diphosphite, tetra(2,3-dichloropropyl) 2-hydroxypropylene diphosphite, tetra (2,3-dich1oropropyl) l-hydroxypropylene diphosphite. By replacing the glycerine with trimethylolethane, trimethylolpropane or 1,2,6-hexanetriol analogous compounds percent prepared including tetra (2-c hlor0ethyl) 2-hydroxymethyl Z-methylpropylene diphosphite, tetra (2'-chloroethyl) 2-hydroxymethyl-2- ethyl propylene diphosphite, tetra (2-bromoethy1) 2-hydroxymethyl-2-methyl propylene diphosphite, tetra (2',3-dichloropropyl) 2-hydroxymethyl-2-methyl propylene diphosphite, tetra (2'-chloroethyl) 6- hydroxy-l ,2-hexy1ene diphosphite, tetra 2'- chloro'ethyl) 2-hydroxy- 1 ,6-hexylene diphosphite, tetra (2'-fluoroethyl) 2-hydroxypropylene diphosphite.

Likewise the corresponding phosphonates of the trimethylolethane diphosphites, trimethylolpropane diphosphites and hexanetriol diphosphites can be prepared in the manner set forth above.

EXAMPLE 33 450.9 grams moles) of bis(2-chloroethyl) phosphorochloridite and 0.35 liter of diethyl ether were added dropwise over a period of2 hours under nitrogen into a mixture of 212.2 grams (2.0 moles) of diethylene glycol and 202.0 grams (2.0 moles) of triethylamine while maintaining the temperature at to C. with an ice-water bath. The mixture was filtered to remove the triethylamine hydrochloride. The filtrate was flash evaporated to remove the ether and obtain bis(2- chloroethyl) hydroxyethoxyethylphosphite as a clear, colorless liquid in a yield of 647.0 grams, iodine number 64.63, C 34.46%, H'6.36%, Cl 23.40%, P 8.23%.

EXAMPLE 34 2,677.9 grams (9.0 moles) of bis(2-chloropropyl) 2- chloroethyl phosphite was mixed with 955.] grams (9.0 moles) of diethylene glycol at 25C. under a nitrogen atmosphere and then distilled at aresidue temperature of 6077C. for 1.75 hours anda distillate temperature of 60-63C. at 575-48 mm.:to obtain 727.0 grams of 2-chloroethanol. The clear, golden-yellowv residue weighed 2,903.0 grams, had an iodine number of70.2l (theory 78.5) and was bis( 2-chloropropyl) hydroxyethoxyethyl phosphite, C 35.72%, H 6.43%, Cl 27.49%,'

EXAMPLE 35 696.5 grams of bis(2-chloropropyl) hydroxyethoxyethyl phosphite prepared in Example 34 was heated in a nitrogen atmosphere at 160C. for 6 hours to get an iodine number of 14.7. It was heated for 6 more hours at C. The liquid product weighed 897.0 grams, had an iodine number of 12.60 and analyzed C 34.37%, H 5.85%, Cl 21.80%, P 10.26% and was primarily 2-chloropropyl hydroxyethoxyethyl 2- chloropropane phosphonate with a small amount of dimer phosphonate and non-rearranged phosphite.

EXAMPLE 35(a) Bis (2-chloroprophyl) hydroxypropoxypropyl Phosphite 560.83 grams (1.8 moles)-of tris (2-chloropropyl) phosphiteand 241.52 grams of dipropylene glycol were mixed at room temperature. The mixture was heated gradually in 2 hours to a maximum residual temperature of 100 C., while removing 177.3 grams (1.87 moles) of 2-chloro-l-propanol by distillation at a vapor temperature of 53 C./44 mm. to 67 C./58 mm.

The residue contained dipropylene glycol bis (2- chloropropyl) phosphite as the main product. It was obtained as a clear, colorless liquid, yield 627.8 grams (99percent). It analyzed C 41.00% (theory 41.02%), H 7.20 (theory7.18%),'

Cl 20.21% (theory 20.18%), P 8.85% (theory 8.82%), Oxygen (by difference)22.74% (theory 22.80%), Iodine number 69.3 (theory 72.2). The iodine number showed that the phosphite had not rearranged to the corresponding phosphonate during the reaction.

EXAMPLE 35(b) good physical properties was 0.5-0.7percetn P in the final foam composition, and for self-extinguishing flexible polyurethane foams, 1 percent P in the final composition.

Hexachlorocyclopentadiene, hexabromocyclopentadiene and hexafluorocyclopentadiene react with vinyl 2-chloroethyl ether in the DielsAlder reaction (or with the corresponding vinyl 2-bromoethyl ether or vinyl 2-fluoroethyl ether) to form 1,4,5,6,7,7- hexachloro-S-norbornen-2-yl 2-chloroethyl ether (or its bromine-containing or fluorine-containing analogues). These compounds when heated with tertiary phosphites of the formula (R 0); form phosphonates of the formulai z l /OR.'.

or in general c1 o1 y g ocmomoomcmon 1 is prepared by reacting one mole of the h bornenyl 2-chloroethyletherwith bis(2-chloroethyl) hydroxyethoxyethyl phosphite. In similar fashion there are prepared methyl hydroxypropoxypropyl l,4,5,6,7,-

exachloronor-' 7-hexachloro-5-norbomen-2-oxyethane phosphonate,

2-bromoethyl hydroxydiethoxyethyl hexabromonorbornenoxyethane phosphonate, 3-chloroethyl 4- hydroxybutyl hexafluoronorbornenoxyethane phos-' phonate.

EXAMPLE 36 Hexachloronorbornenyl chloroethyl ether. 136.4grams (0.5mole) of hexachlorocyclopentadiene and 0.6 grams of 2,6-di t-butyl-4-methylphenol Y were added 52.8 grams (0.495 mole) of vinyl 2- ehloroethyl ether. The mixture was heated at l15-l44C. for 6hours. The product was then distilled, first at the water pump to remove volatiles at a temperature up to C. and then in a high vacuum. The cut boiling at 107C. at 0.135 mm. to 120C. at 0.16 mm. and weighing 130.7 grams was collected. The analysis was C 28.53%, H1.82%, Cl 65.59%, 0 (by difference) 3.95which coincides closely with'thc theoretical values for C,H-,0Cl-,', hexachloronorbornenyl chloroethyl ether. v

Tris(2-chloroethyl) phosphite heated mole for mole with N,N-dimethylaniline (45-70C.) in xylene as a solvent dehydrochlorinates to bis(2-chloroethyl) vinyl phosphite. Heating this compound with hexachlorocyclopentadine gives bis (2-chloroethyl) 1,4,5,6,7,7- hexachloro-S-norbornen-2y l phosphite. Transesterification of this on a mole to mole basis with dipropylene glycol by heating below 100C. with alkaline catalyst gives'2-chloroethyl hydroxypropoxypropyl l,4,5,6- ,7,7-hexachloro-5-norbomen-2-yl phosphite of the formula When the transesterification with the diol is carried out with heating above 100C. (either with or without ClCH,CH,Clas a catalyst) rearrangement to the corresponding phosphonate 'occurs. Thus heating bis(2- chloroethyl l,4,5,6,7,7-hexachlord-S-norbornen-2-yl phosphiteto C; with an equimolar amount of diethylene f glycol gives hydroxyethoxyethyl 1,4,5,6,7,7-

hexachloro-5-norbornen-2-yl 2-chloroethane phosphonate. Similarly there are obtained hydroxypropoxypropyl 1,4,5 ,6,7,7-hexachloro-5-norbornen-2-yl 2- chloroethane phosphonate, hydroxydiethoxyethyl 1,4,- 5,6,7,7-hexachloro-5-norbornen-2-yl 2-chloro-ethane phosphonate, hydroxypropoxypropyl l,4,5,6,7,7- hexachloro-S:norbornen-2yl 2-bomoethane phosphonate, hydroxypropoxypropyl l,4,5,6,7,7-hexabromo-5- norbornen-2-yl 2-chloroethane phosphonate, and hydroxy-ethoxyethyl 1 ,4 ,5 ,6,7,7-hexabromo-5- norbornen-Z-yl Z-bomoethane phosphonate.

When bis(2-chlorethy1) vinyl phosphite (or the corresponding bis(2-bromoethyl) vinyl phosphite) is heated mole for mole with hexachlorocyclopentadiene (or the bromo analogue) above 100C., e.g. to C.

there is formed the corresponding phosphonate: bis(2- chloroethyl) l,4,5,6,7,7-hexachloro-5-norbornene-2- phosphonate (or bromine analogues). Upon heating with 1 mole of a diole such as diprophylene glycol or diethylene glycol there is obtained 2-chloroethyl hydroxypropoxypropyl l,4,5,6,7,7-hexachloro-5- norbornene-Z-phosphonate, 2-chlorethyl hydroxyethoxyethyl l,4,5 ,6,7,7-hexachloro-5-norbornene-2- phosphonate, 2-bromoethyl hydroxy-propoxypropyl 1,4,5 ,6,7,7-hexabromo-5-norbornene-2-phosphonate.

alcohol, butyl alcohol, decyl alcohol, phenol, chlorophenol or the like gives the compound- T Vinyl dlchlorophosphonate CHa=CHP I OR 01 (or the bromine analogue). Heating one mole of this compound with one mole of a diol such as diethylene glycol or dipropylene glycol and distilling off the monohydric alcohol or phenol gives products including methyl hydroxypropoxypropyl l,4,5,6,7,7-hexachloro- -norbornene-2-phosphonate, decyl hydroxyethyoxyethyl 1,4,5 ,6,7,7-hexachloro-5-norbornene-2- phosphonate, phenyl hydroxypropoxypropyl 1,4,5,6,7,- 7-hexachloro-5-norbornene-Z-phosphonate, octyl hydroxyethoxyethyl l,4,5,6,7,7-hexabromo-5- norbornene-Z-phosphonate or the like. In this reaction preferably there are at least 4 atoms in the chain between the two hydroxyl groups of the diol reactant to avoid ring formations. Reacting one mole of l','4,5,6,7,- 7-hexachloro-5-norbornen-2-yl dichlorophosphonate with a mixture of 1 mole of an alcohol (or phenol) R OH and one mole of a diol, HOR,Dl-l, e.g. dipropylene glycol or diethylene glycol forms the same product directly but with impurities since in addition to forming the desired compound There are also formed 0 R1 O RnOH and R -P where R13 is the l,4,5,6,7,7-hexachloro-5-norbornen- 2-yl group, R, is alkyl or aryl and R alkylcne of at least two carbon atoms (and preferably at least 4 carbon atoms), alkyleneoxyalkylene, or poly(alkylcneoxy) n|- kylene.

The same compounds can be prepared by the Arbuzov reaction of l,4,5,6,7,7-hexachloro-2-bromo-5- norbornene with a phosphite having the formula (ROhPOR where R is aryl and R is hydroxyalkyl or hydroxyalkoxyalkyl or hydroxy(polyalkoxy)alkyl and removing one mole of RBr, e.g. by distillation, In addition to the compounds mentioned above by this procedure there can be obtained, for example, ethyl hydroxyethyl l,4,5,6,7,7-hexachloro-5-norbornene-2 -phosphonate. These same compounds also can be prepared by reacting hexachlorocyclopentadiene (or Hexabromocyclopentadiene) with a compound where R is alkyl or aryl and R is hydroxylkyl, e.g. hydroxyethyl or hydroxypropyl or hydroxyalkoxyalkyl, e.g. hydroxyethoxyethyl or hydroxypropoxypropyl.

Likewise the compounds can be prepared by reacting 1,4,5 ,6,7,7-hexachloro-5-norbornen-2ol (or the corresponding hexabromo or hexafluoro analogues) with a tertiary phosphite of the formula where, R, and R, are loweralkyl, lower alkenyl; lower haloalkyl, or lower haloalkenyl, e.g., methyl, ethyl, butyl, 2-chloroethyl, 3-bromopropyl, 2-fluoroethyl, allyl, 2'-bromoallyl and RR, is lower alkylene of at least 2 carbon atoms, e.g. ethylene, propylene, butylene and n is an integer of l, 2, 3, 4, e.g., hydroxybutyl, hydroxyethoxyethyl, hydroxypropoxypropyl esters. The resulting hexahalonorbornenyl alkylhydroxyalkyl phosphites are rearranged by heating over C to the corresponding phosphonates.

EXAMPLE 37 The compound 1,4,5 ,6,-7,7 -hexachloro-S-norhornen- 2-ol is prepared as follows:

Hexachlorocyclopentadiene was reacted with vinyl acetate by the Dials-Alder procedure to give l,4,5,6,7,-.

ing at l06l 13C. at 0.59-.80 mm. was collected. It

was a clear pale yellow liquid with clear colorless crysv tals. It analyzed correctly for 1,4,5,6,7,7-hexachloro-- norbornen-2-yl acetate. 47.8 grams of this acetate was dissolved in 20 m1. of methanol and 5.3 grams of sodium hydroxide dissolved in 200 ml. of methanol was gradually added. The purple colored liquid formed'was filtered to remove a white solid precipitate'The filtrate was concentrated on a flash evaporator to remove most of the methanol. The product was diluted with 80 ml. of methanol, the solid filtered off and the filtrate concentrated at the water pump to give a brown black oil. The oil was vacuum distilled. The distillate (5.5 grams) at 68-127C. at 1.5-1.7 mm. was collected and redistilled and the cut boiling at 93C. at 0.07 mm. collected. It was a dark red-brown viscous liquid and analyzed C 27.69%, H 1.42%, Cl 65.78%. Itwas 1,4,5,6,7,- 7-hexachloro-5-norbornen-2-ol.

This same compound was obtained in purer form by hydrolysis with HCl in refluxing. methanol for 40 hours. The compound was recovered after removing volatiles at the water pump as a crystalline solid, MP. 6l 58C. by recrystallization from acetone, C 26.59%, H 1.17%, Cl 66.36%.

EXAMPLE 38 200 grams (0.632 mole) of 1,4,5,6,7,7-hexachloro-2- hydroxy-S-norbrnene (M.P. 157159C.) were mixed with 170 grams (0.632 mole) of tris (2-chloroethyl) 'phosphite and heated in a nitrogen atmosphere at 103150C. residue temeprature for 6 hours at 31 to 42 mm. and 4864C. vapor temperature to obtain 21.1 grams of 2 -chloroethanol as the distillate. The residue was a slightly viscous, dark orange brown liquid weighing 329.3 grams. It. had an iodine number of 26.08 (theory 50.2), C 26.55%, H 2.51%, Cl 53.05%, P 6.04%. It was bis(Z-chloroethyl) '1,4,5,6,7,7- hexachloro-S-norbornen-2-yl phosphite (also called HNB-CEP). The product also had considerable phosphonate caused by rearrangement at the high refluxing temperature as shown by the relatively low iodine number. Reaction of the product mole for mole with diethylene glycol or dipropylene glycol and removal of one mole of 2-chloroethanol gives the'corresponding 2- chloroethyl hydroxyethoxyethyl (or hydroxypropoxypropyl) 1,4,5,6,7,7-hexachloro-5-norbornen-2-ylphosphite.

EXAMPLE 39 272 grams (lmole) of hexachlorocyclopentadiene were preheated to 160C. in a nitrogen atmosphere- Then there was added 233 grams (1 mole) of bis(2- chloroethyl) vinyl phosphonate dropwise in a period of 1 hour. The heating was continued after completion of the addition for 4 more hours at 160C. The reaction solution was a dark reddish orange solution. The solution was distilled under vacuum up to a 115C. residue temperature, distillate temperature 76-77C. to 0.05 mm. to remove 48.0 grams of hexachlorocyclopentadiene. Heating was continued at up to 114C. residue temperature at 73-89C. vapor temperature at 0.09 to 0.03 mm. and there was recovered an additional 2.3 grams of hexachlorocyclopentacliene but no bis(2- chloroethyl) vinyl phosphonate. The residue of 448 grams was bis(2-chloroethyl) l,4,5,6,7,7Hexachloro-5- norbornen-2-yl phosphonate (HNB-CET), iodine'number 1.70, C 26.67%, H 2,63%, CL 5245-, P 6.82%. This product which is an isomer of the product of Example 38 can be reacted in the same manner with an EXAMPLE 40 252.9 grams (0.5 mole) of the HNB-CEP formed in Example 38 were mixed with 67.1 grams (0.5 mole) of dipropylene glycol and heated under a nitrogen atmosphere at the water pump to distill out 2-chloroethanol. Distillation was carried out for 1.5 hours at 1'04138C. residue temperature and 65-76C. vapor temperature at 41-33 mm. There were collected 34.5 grams of distillate. The residue was clear, viscous dark orange-brown liquid weighing 280.7 grams. The iodine number was 16.47 (theory 45.35 for the phosphite product) showing that the product was about 36% 2- chloroethyl hydroxypropoxypropyl 1,4,5,6,7,7- hexachloro-5-norbornen2yl phosphite (DPG-HNB- CEP) and 64percent hydroxypropoxypropyl 1,4,5,6,7,- 7hexachloro-5norbornen-2-yl -chloroethane phosphonate. The product analyzed C 31.52%, H 3.73%, CI 43.55%, P 5.31%

EXAMPLE 41 65.0 grams (0.1286 mole) of HNB-CEP and 13.6 grams (0.l286 mole) of diethylene glycol were heated up to C. residue temperature and 6290C.- vapor temperature at 52-48 mm. to distill off 6.6 grams of 2- chloroethanol in 1.5 hours. The residue was a slightly viscous liquid weighing 65.5 grams. It had an iodine number of 19.05 (theory 47.8) and analyzed C 29.88%, H 3.27%, Cl 44.66% P 5.32%. it was a mixture of about 40% 2-chloroethyl hydroxyethoxyethyl l',4,5,6,- 7,7-hexachloro-5-norbornen-2-yl phosphite and 60% hydroxyethoxyethyl 1,4,5 ,6,7,7-hexachloro-5- norbornen-Z-yl 2-chlorethane phosphonate.

Example 42 392.6 grams (1.456 moles) of tris(2-chloroethyl) phosphite and 482.0 grams (1.456 moles) of 1,4,5,6,7,- 7-hexachloro-2-methylol-5-norbornene were heated under nitrogen at 18.50 mm. up to C. residue temperature while distilling off liquid including 2- chloroethanol at 60C. and 48 mm., 183C. at 35 mm. and 100C. at 18 mm. Total distillate was 77.5 grams. Distillation was continued for hours up to 142C. residue temperature to obtain 36.2 grams more of distillate. The residue was a nearly colorless, slightly orange, slightly viscous liquid in an amount of 741.1 grams. it had an iodine number of 36.41 (Theory 48.8), C 27.54%, H 2.40%, C] 52.63%, P 5.35% and was bis(2- chloroethyl) 1,4,5 ,6,7,7-hexachloro-5-norbornen-2- ylmethyl phosphite with a small amount of 2- chloroethyl 1,4,5 ,6,7,7-hexachloro-5 -norbornen-2- ylmetliyl 2-chloroethane phosphonate.

EXAMPLE 43 ange liquid weighing 396.4 grams. It had an acid num-' ber of 3.92 (theory zero) and iodine number of 29,71

(theory 44.25) and was approximately 67% 2- chloroethyl hydroxypropoxypropyl 1,4,5,6,7,7- hcxachloro-S-norbornen-2-ylmethyl phosphite and 33% hydroxypropoxypropyl l,4,5,6,7,7-hexachloro -5-norbornen-2-ylmethyl 2-chloroethane phosphonate. The analysis was C 33.33%, H 3.46%, Cl 43.73%, P 5.57%.

EXAMPLE 44 The product of Example 43 was heated under nitrogen for 10.5 hours at l55C. The resulting material was a nearly clear, viscous organic liquid. The iodine number was 10.55 indicating that the product was approximately 75% hydroxypropoxypropyl l,4,5,6,7,7- hexachloro-S-norbornen-2-y1methyl 2-chloroethane phsophonate and 25 percent the starting phosphite. The analysis was C 32.64%, H 3.75%, Cl 43.32%, P 5.75%.

Hexachlorocylopentadiene and piperylene from the Diels-Alder adduct (PNB) 01 C1 CH=CHCH3 (5-( l'-propenyl-)1,2,3,4,7,7-hexachloro-2- norbornene) (and a small amount of its isomer). This is then reacted mole for mole with bromine or chlorine In a specific example to 170.5 grams (0.5 mole) of the Diels-Alder adduct of hexachlorocyclopentadiene and piperlene a plae yellow liquid) there was added 0.5 mole (plus 0.9 gram excess) of bromine in 330 ml. of carbon tetrachloride with cooling and stirring over 5 hours. The temperature was kept at l9-35C. The solvent was distilled off to recover the dibromo compound as a high-boiling, golden yellow liquid, 5-(l',2' -dibromopropyl) l,2,3,4,7,7-hexachloro-2- norbornene.

This product when heated mole for mole with dinlkyl hydroxylakyl phosphites or dialkyl hydroxyalkoxyalkyl phosphites forms isomeric mixtures of monohydroxy phosphonate, e.g. with diethyl hydroxypropoxypropyl phosphite there is obtained.

20 and its positional isomer with the bromine atom on the carbon atom adjacent to the phosphorus atom.

EXAMPLE 46 PNB (5-(l'-propenyl-) l,2,3,4,5,6,7,7-hexachloro-2- norbornene) in an amount of 340.9 grams (1.0 mole) was placed in a flask together with 400 ml. CCL. (solvent) at room temperature. There was added 75.9 grams (1.07 mole) of chlorine (C1 at 26 to 55C. gradually over 5.5 hours. The solvent'was recovered by flash distillation and distillation at the water pump. The residue was subject to vacuum distillation. The cut having a B.P. 127-l32C. at 0.19 mm. in a yield of 149.6g. analyzed C 20.06%, H 2.03%, Cl 68.05% and was 5- (1'2' -dichloropr0pyl) l,2,3,4,7,7-hexachloro-2- norbornene (PONB). The cut immediately preceding this, B.P. (0.3 mm.) to 133C. (0.22 mm.), 149.6 g., was the same product with a trace of starting PNB. Two other cuts which included the PONB together with minor amounts of impurities weighed 60.5 grams.

Tris (haloalkyl) phosphites, e.g. tris(2-chloroethyl) phosphite, tris(2-bromoethyl) phosphite, tris (2- bromopropyl) phosphite, tris(2-fluoroethyl) phosphite, tris(2,3-dichloropropyl)phosphite, tris(2- chloropropyl) phosphite when heated, e.g. to 150C. with dihalopropionitriles, e.g., alpha,. betadichloropropionitrile, alpha, beta-dibromopropionitrile and alpha, beta-difluoropropionitrile formed phosphomates in the following fashion oiomomom CICHZCHCIGN H (ClCHzCHzOhPCHzCHClCN (together with its isomer 0 (CIOHaOHaOlz CHCN) These phosphonates in turn are heated with an equim 0- lat amount of a diol HO(R'O),,H to form phosphonates such as H CICHaCHzO P-CHzCHCN HOOH;CH2OCH2CH: 1

e.g. 2'-chloroethyl hydroxyethoxyetliyl 2-chloro- 2- cyanoethane phosphonate, 2'-chloroethyl hydroxyethoxy-etl1yl 2-chloro-l-cyanoethane phosphonate, 2'- bromoethyl hydroxypropoxypropyl 2-chloro-2- cyanoethane phosphonate, 2'-fluoroethyl hydroxybutyl 2-bromo-2-cyanoethane phosphonate, 3-chloropropyl hydroxypropoxypropyl 2-chloro-1-cyanoethane phosponate.

EXAMPLE 47 Bis(2-chlorethyl) chlorocyvunoethane phosphonatc.

317.7 grams (2.663 moles) of alpha, betadichloropropionitrile were mixed with 177.] grams of 2chlorethanol (solvent) and 898.9 grams of bis(2- ethoxyethyl) ether (solvent). The mixture was heated to C. under nitrogen until slow distillationof the 2-chloroethanol started and there wasv then addeddropwise 691.5g. (2.563 moles) of tris(2-chlorethyl) phosphite over 2hours. The reaction mixture temperature was held at 130-150C. while the vapor temperature was about 90l 18C. Heating was continued for another half hour at about C. (reaction mixture) at which time a total of 230 ml. of distillate had collected. Distillation was then continued at the water pump until the bis(ethoxyethyl)ether was recovered. The residue was filtered and distillation was then resumed at about 0.4 to 1.6 mm. to recover unreacted tris(2-chloroethyl) phosphite. The residue was crude 5 bis(2-chlorethyl) chlorocyanoethane phosphonate, a dark brown viscous oil weighing 528.6grams. A portion (63.2 grams) of this was subjected to distillation in a micro apparatus. The residue from the distillation was called CNB is made by condensing 2 moles of hexachlorocyclopentadiene with 1 mole of 4- vinylcyclohexene. It reacts with two moles of chlorine OPP-R5 1 (even if excess chlorine is used) to give dichloro CNB shown below and two moles of gaseous HCL ll l (:1 c1 I (1| l 01 Cl w (and isomors of (lg Cl Cu 'lioOlul The corresponding tetradecabromo compounds can also be prepared by adding bromine to the bromo ana- 6 logue of CNB. The product reacts with dialkyl hydroxyalkyl phosphites or dialkyl hydroxyalkoxyalkyl phosphites or the corresponding di(haloalkyl) or di(- haloalkoxyalkyl) or di(haloalkoxyalkyl) hydroxyalkoxyalkyl phosphites to form the corresponding phosphonates in the Arbuzov reaction by heating to about C. Thus there can be prepared chloroethyl hydroxyethoxyethyl dichloro CNB phosphonate, bromoethyl hydroxypropoxypropyl dichloro CNB phosphonate, fluoroethyl hydroxyethyl dichloro CNB phosphonate. The l:] adduct of 4-vinylcyclohexene and hexachlorocyclopentadiene (1,4,5,6,7,7-hexachloro-2-(3 cyclohexenyl)-5-norbornene) (also called HCNB) as well as CNB itself (and their bromo and fluoro analogues) react with tertiary phosphites (R 01 where R, is as defined above to form phosphonates such as dimethyl CNB phosphonate, diethyl CNB phosphonate,

di(2-chloroethyl) CNB phosphonate, di(Z-bromoethyl) CNB phosphonate, di(beta-chloroethyl) 1,4,5,6,7- pentachloro-2-(3'-cyclohexenyl)-5-norbornene-7- phosphonate. These products in turn can be transesterified with one mole of a diol HO(RO),,H where R and n are as previously defined to give products such as ethyl hydroxypropoxypropyl CNB phosphonate, 2- chloroethyl hydroxyethoxyehtyl CNB phosphonate, 2- bromoethyl 4-hydroxybutyl CNB phosphonate, 2- chloroethyl hydroxydiethyoxyethyl bromo CNB phosphonate, ,Z-fluoroethyl hydroxypropoxypropyl fluoro CNB phosphonate, 2-chloroethyl hydroxyethoxyethyl 1,5 ,6 ,7 ,7- pentachlor o-2,-( 3 "-cyclohexenyl)-5- norbornene-7-phosphonate. Some representative equations with-HCNB are as follows:

out'onn' For'CNB the product is Cl Cl\ Of course, the products are formed as a mixture of isomers. Thus in the CNB product the phosphorus atom can be attached in the other chlorinated norbornene ring. The various stereo isomers also are formed simultaneously.

Similar products can be produced by reacting one mole of 4-vinylcyclohexane with 2 moles of pentachlorocyclopentadiene phosphonate of the formula where R is as define?!"abbb'iWEEYduct When one mole of this product is heated with one mole of diol there is formed a monohydric alcohol of the present invention. In the formulae the chlorine atoms can be replaced by fluorine or bromine.

Likewise the addition product of 1 mole of chlorine (or bromine) with HCNB (or its bromo or fluoro analogues) and having the formula (called HDNB) reacts in the Arbuzov reaction with tertiary phosphites of the formula to form hydroxyphosphonates including 2-cl1loroethyl hydroxyethoxyethyl 1,2,3,4,7,7-hexachloro-5-(lchlorocyclohex-4-yl) 2-norbornene 2-phosphonate (2- chloroethyl hydroxyethoxyethyl HDNB phosphonate), 2-chloroethyl hydroxypropoxypropyl 1,2,3,4,7,7- hexachloro-5-( 1 '-bromocycl0hex-4'-yl) 2-norbornene 2-phosphonate, ethyl hydroxy-dipropoxypropyl l,2,3,4,7,7-hexabromo HDNB phosphonate, 2- bromoethyl hydroxypropoxypropyl 'HDNB phosphonate. 1

Example 47(0) CNB 3.5 moles (378.6 grams) of 4-vinyl-l-cyclohexene and 2 grams of 2,6-di-t-butyl-4-methylphenol (an antioxidant) were mixed at room temperature and heated 24 to 128C. in a nitrogen atmosphere. To this solution was added dropwise 1909.6 grams (7.0 moles) of hexachlorocyclopentadiene while the temperature rose, first from external heating and then due to the exothermic action, from about 128C. to 148C. The addition was completed in 5 hours and 45 minutes at this temperature. The orange colored liquid was heated, for a further 14 hours at about 145C. The reaction product was poured hot and after some cooling mixed with grams of petroleum ether (B.P. 3060C.) and with 785 grams of isopropyl alcohol, whereupon the principal product of reaction, the 2:1 molaradduct of C C1 to 4-VCH designated CNB (or C H C1 precipitated as a white crystalline solid and was isolated by filtration. After washing with 400 grams of isopropyl alcohol and drying in a vacuum oven at 25C./0.5 mm. over Drierite for 2 days a first crop of CNB of 1 159.0 grams was obtained, M.P. 203-212C. The total yield obtained including an additional crop isolated by concentration of the filtrate and dilution with isopropyl alcohol was 2194.9 grams which after one crystallization had a M.P. 212-231C. Recrystallization from nheptane (or from acetone) using some activated carbon to absorb traces of impurities gave analytically pure CNB white crystals M.P. 238243C. to a colorless liquid without decomposition. CNB hasthe chemical name 6-(1', 2', 3', 4, 7', 7' Hexachloro-2'-norbornen-5'-y1-) 1,2,3,4,9, 9-hexachloro- 1,4,4a,5 ,6,7,8,8a-octahydro-1,4- endomethylenenaphthalene1 ln asimilar fashion there is prepared the 1:2 adduct of d,1-limonen (dipentene) with hexachlorocyclopentadiene according to the equation OI CH3 A C1 C1 =CH; C1 Cl CH:

l Wu it 1 m .r

The adduct occurs as a mixture of stereoisomers. The 1:1 adduct of dipentene and hexachlorocyclopentadiene was also prepared. Both of these adducts were useful in making phosphites and phosphonates analogous to those obtained from CNB.

The 1:1 adduct of vinyl cyclohexene and hexachlorocyclopentadiene (HCNB) is obtained as a minor by-product (about 3 percent) as a forerun in the distillation to recover CNB. It can be obtained in higher yields by carrying out the same reaction but starting with either a 1:1 mole ratio or a 2:1 mole ratio of vinyl cyclohexene and hexachlorocyclopentadiene. It was a pale yellow liquid distilling at 132C./O.l4 mm. to 144.5C./0.2 mm.

25 Example 47(b) There were employed 173.1 grams (1.6 moles) of hexachlorocyclopentadiene, 873.0 grams (3.2 moles) of 4-vinyl cyclohexene and 20.9 grams (2.0% by weight of total reactants) of tris (2-chloroethyl) phosphite. The total amount of 4-vinylcyclohexene was heated under a nitrogen atmosphere with stirring and reflux to a predissolved mixture of one-half of the hexachlorocyclopentadiene and one-half of the tris (2-chloroethyl) phosphite were added dropwise at 120160C. in about 2 hours. The mixture was then heated lthour at 170C., cooled at 160C. in about 10 minutes and the remaining half of the hexachlorocyclopentadiene and tris(2-chloroethyl) phosphite added over about 3 hours. Heating was continued at 160C. for an additional 6 hours. The mixture was cooled to about 1 10C. and poured into 1.0 liter of isopropanol. The crystals (544.0 grams) were CNB. The filtrate together with washings from the crystals was concentrated at about 45C. to obtain a very viscous light brown oily liquid which was poured into a tray, transferring with petro leum ether and allowing the petroleum ether to evaporate. Then added 400 ml. of isopropanol to obtain 38.8 grams more of crystalline CNB. The oil remaining after filtering off the CNB was concentrated to give 466.9 grams which contained the Michaelis-Arbuzov type phosphonate reaction products of tris (chloroethyl) phosphite with (1) CNB and (2) HCNB.

EXAMPLE 47(c) Example 47(b) was repeated replacing the 2 percent of tris (2-chloroethyl) phosphite by 2 percent of tris (dipropylene glycol) phosphite. After removal of the CNB crystals the residual oil weighed 466.9 grams and contained the Michaelis-Arbuzov type phosphonate reaction products of tris (dipropylene glycol) phosphite with (1) CNB and (2) HCNB.

ln examples 47(b) and there was no need to isolate the individual phosphonates prepared since in each one the mixture was effective in making selfextinguishing and fire retardant polyurethane foams.

EXAMPLE 4:;

Dichloro CNB 0.5 mole (326.85 grams) of CNB or C l-I Cl a white crystalline solid, was dissolved in 1000 ml. of carbon tetrachloride and 6 m'oles (425.4 grams) of chlorine (C1 were added in the presence of ultraviolet light at room temperature to reflux temperature for 4 hours and then at reflux temperature for 28.5 hours. The product was evaporated to remove carbon tetrachloride, chlorine and HCL. The slightly gummy, amher-colored solid obtained was dissolved in 1500 ml. of acetone and filtered through activated charcoal. The liquid was flash-evaporated to give a viscous liquid which precipitated in about 350 ml. of isopropanol. The off white elastic mass was dried to give 369.5 grams of product which was recrystallized from acetone by adding isopropanol. It melted at 97-110C. The analysis of the dichloro CNB product was C 29.78%, H 1.46%, Cl 69.04%. which agreed quite closely with theoretical for C I-1 C1 EXAMPLE 49 Hexachloro (dichlorocyclohexyl) norbornene.

327.9 grams (0.861 mole) of HCNB, a pale yellow clear liquid, was placed into a flask with 1.2 liters of CCl as a solvent. There was then bubbled in 62.9 grams (0.887 mole) of chlorine gas at room temperature over a period of4 hours and 10 minutes. The temperature was kept below 40C. The solution was flashevaporated to 400 ml. The volatiles were then removed at the water pump. The product was primarily hexachloro(dichlorocyclohexyl)norbornene (HDNB) mixed with some starting hexachloro(cyclohexenyl)norbornene (HCNB) and a small amount of dimerized starting material.

One mole of 1,2,3,4,5-pentach1oro-l-(betachloroethyl) 2,4-cyclopentadiene reacts with one mole of 4-vinylcholorhexene to form (also called 1 ,4, 5, 6,7 -pentaeh1oro-7-beta-chloro-thy1-2- (3'-cyclohexeny1) -5-norbornene) when two Yn oles of the chlorinated cyclopentadiene compound are reacted with one mole of 4- vinylcholohexene; the product is Analogous products having-halogen substituted aliphatic rings are formed by reacting 1,2,3,4,5- pentabromo-l (betachloroethyl) cyclopentadiene with one or two moles of 4-vinylclohexene. Compounds l and II and their analogues mentioned above react with tertiary'phosphites, ofv the formula (RO),P, e.g. at 140C., in the Arbuzov reaction to form phosphonates of the formula f I v g 0 momma; 011" and Rtcmomg on by the reactions "merrrem'cnr R 01.1w 1

R7CH2CII2P(OR")2 RC1 and Rsomcmcl (RO)3P where R,CH,CH,C1 is compound land R CH,CH Cl is compound II and R" is alkyl, alkenyl, haloalkyl or ha- ,loalkenyl, e.g. methyl, ethyl, butyl, allyl, methallyl,

chloroethyl, chloropropyl, fluoroethyl, bromoethyl, 2-

chloroallyl. All of the R" groups can be the same or different. The phosphonate esters thus prepared can be transeseterified with diols, e.g. 1,4-butanediol, diethylene glycol, dipropylene glycol, triethylene glycol or tripropylene glycol by simply heating the phosphonate and diol in equimolar amounts and distilling off the monohydric alcohol formed, e.g.

O RaCH2CHz-O CHQCHZOCHQCHQOH CHgCHgCl and the corresponding compounds where the chlorine atoms in R are all replaced by either bromine or fluorine, as well as the corresponding compounds where the transesterifying diol is dipropylene glycol or triethylene glycol and R is methyl, fluoroethyl, 3-

chloropropyl, ethyl, or butyl.

EXAMPLE 49(a) O T (ClOH2CHzO)g-P-Ol One mole (269.5 grams) of tris (2-chloroethyl) phosphite was added dropwise to the solution of one mole (272.8 grams) of hexachlorocyclopentadiene in one liter of commercial grade xylene. Initially, the phosphite was at 25C. and the xylene solution at 55C. During the addition which took about 1 hour the color of the mixture changed gradually from pale yellow to golden yellow and then to black. After the addition of 55C., the mixture was heated to 70C. whereupon an exotherm resulted and the temperature reached 105C. The mixture was cooled externally and then reheated to C. It was kept at this temperature for a total of 6.5 hours. Then the products were separated by fractional distillation.

The first fraction was xylene which was recovered quantitatively. The second, small fraction was a mixture of recovered hexachlorocyclopentadiene and 1- (beta-chloroethyl 1 ,2,3,4,5-pentachlorocyclopentadiene-2,4, which latter compound wasdesignated CEPC. This fraction boiled at 88C./2.0 mm. to 106C./2.3 mm. The yield was 71.9 grams of a pale yellow liquid.

The third and most important fraction contained both CEPC and bis(2-chloroethyl) phosphorochloridate designated BCEP. This fraction was a pale yellow liquid distilling at 108C./2.2 mm. to C./3.4 mm. The crude yield was 245.6 grams. (Theoretical :yield of CEPC 300.85 grams or 1 mole.)

The fourth fraction was 32.5 grams of an orange colored liquid, B.P. 138C./3 mm. to 163C./4 mm. and contained mostly BCEP. The fifth fraction was a brown black viscous, pourable, undistillable residue, 180 grams.

The third fraction which contained the major amount of the desired product CEPC was redistilled fractionally. Before the fractionation the weight was 245.6 grams and all products weighed 243.45 grams (including 0.95 gram of an undistillable residue), so the volatilization losses in the refractionation were only 2.15 grams.

This second fractional distillation yielded four distilled fractions and the residue. The major fractions were the second fraction (189.6 grams) and the third fraction (32.9 grams) both of which were pale yellow liquids. The second fraction was essentially CEPC with a small amount of BCEP. It distilled at 96-102C./0.38 mm. and analyzed C.25.82%, H 1.61%; Cl 67.49%, molecular weight 285 (in chloroform solution). Theory for C H Cl are C 27.95%, H 1.34%, Cl 70.71%, molecular weight 300.85.

The third fraction was a mixture of CEPC and BCEP.

EXAMPLE 50 158.4 grams (0.527 mole) of l-(beta-chloroethyl)- l,2,3,4,5-pentachlorocyclopentadiene, a pale yellow liquid, were mixed with 28.2 grams (0.26 mole) of 4- vinyl-l-cyclohexene at room temperature and heated to 130C. and kept at 130l54C. for 9 hours. The temperature was then raised to about C. and held there for an additional 5 hours and 20 minutes. The product was then vacuum distilled. The forecut was discarded. The fraction having a B.P. of 174C./0.81 mm. to 198C./4.1 mm. was the 1:1 adduct (compound I, C H CI a clear yellow liquid analyzing C 42.72%, H 4.43%, Cl 52.58%, R.I. 1.555 at 26C., density 1.1545 at 25.5C. and in an amount of 47.7 grams.

After removing compound I by distillation a small amount of additional distillate was recovered (about 3 grams). The residue was very viscous and dark brownblack when poured at 100C. into a beaker. It solidified to give 62.0 grams of solid. The solid was dissolved in 500 ml. of acetone and the insolubles filtered off. The

clear dark brown filtrate was filtered over charcoal, 100 ml. n-heptane added and the solution concenrated on a flash evaporator to 90 ml. The clear brown viscous solution was dissolved twice in ethyl ether and precipitated in aqueous isopropanol vto obtain a light tan colored solid. This first solid weighted 8.3 grams dry and had a MP. of 73-78C. The filtrate was treated with water and NaCl to obtain a second crop of solid. The

second solid had a MP. of 62-70C. The first solid analyzed C 38.92%, H 3.09%, Cl 58.04% while the second solid analyzed C 37.86%, H 3.11%, Cl 59.03%. Both of these solids were the 2:1 adduct (compound ll, C H Cl of different degrees of purity, the second solid being in the purer condition.

Alphawhloroacrylontrile was heated with hexachlorocyclopentadiene to form l,2,4,5,6,7,7- heptachloro-2-cyano-5-norbornene of the formula CN 01 01 c1 (HEBT) C1 01 H H in a specific reaction there was used 818.4 grams of hexachlorocyclopentadiene, 262.6 grams of alphachloroacrylonitrile and 1.1 grams of hydroquinone (as a polymerization inhibitor). The reaction was carried out in a closed one liter steel reactor. The reaction vessel was heated over a period of 2 hours to 164C. at which time heat was shut off as the exothermic reaction had begun. The pressure in the vessel rose to a maximum of 265 psi in another 10 minutes and then gradually subsided. After cooling and release of pressure, the.

product was heated on a water bath, filtered hot, the filtrate cooled to form a solid and the solid dissolved in 3 liters of heptane at 60C. Undissolved matterwas filtered off. The filtrate was concentrated by flash evaporation to give crude HEPT in a yield of 515.2 grams as tan-white solid crystals. These were recrystallized from heptane to give crystalline HEPT M.P. l74l76C.

This compound (and its bromine analogue l,2,4,5,6,- 7,7-heptabromo-2-cyano-5-norbornene as well as 1,4,- 5 ,6,7,7-hexachloro-2-bromo-2-cyano-5-norbomene) are also useful for forming monohydroxyphosphites and phosphonates. Likewise there can be used These two isomers are formed togetheras a yellow high boiling liquid by reacting one mole of hexachlorocyclopentadiene with one mole of a mixture of Z-methyl- S-chloro-S-cyano-l-cyclohexene and l-methyl-S- chloro-S-cyano-l-cyclohexene (the mixed cyclohexenes being prepared from equimolar amounts of isoprene and alpha-chloroacrylonitrile). The isomeric mixture after the reaction with C Cl, is designated MHEPT.

- One mole of HEPT was a heated for 8 hours at l40l 80C. with one mole of tris(2-chloroethyl) phosphite and the 1,2-dichloroethane formed distilled out to form in 98 percent yield bis(2-chloroethyl) HEPT 5 phosponate a yellow liquid of the formula 01 ON C. Q o 10 l T 01 C1 P-(O 011 011201 By using tris (2,3-dichloropr0pyl) phosphite there is obtained bis(2,3-dichloropropyl) HEPT phosponate, and similarly there are prepared bis(2-bromoethyl) HEPT phosphonate and bis(3-choropropyl) HEPT phosphonate. Preferably there is included an inert solvent, e.g. xylene.

The corresponding compounds are formed when MHEPT is used in place of HEPT, e.g. bis(2- chloroethyl) MHEPT phosphonate, bis(2,3- dichlorOpropyl) MHEPT phosphonate.

'These" phosphonate products from HEPT and MHEPT are then heated with an equimolar amount of a diol (preferably in the presence of a small amount, e.g. 0.01 mole of alkaline catalyst, e.g. sodium butylate), and the chlorohydrin formed removed by distillation. Thus, heating 1 mole of bis(Z-chloroethyl) HEPT phosphonate with 1 mole of dipropylene glycol and removing the ethylene chlorohydrin by distillation gives 2-chloroethyl hydroxypropoxypropyl HEPT phosphonate of the formula 01 'cN O1 0 CH; cm 40 T A A PO Heirloom HOH 01 C1 cmomcl Similarly there are obtained 2-chloropropyl hydroxyv propoxypropyl HEPT phosphonate, 2-chloroethyl hydroxyethoxyethyl HEPT phosphonate, 2-chloroethyl hydroxybutyl HEPT phosphonate, 2-bromoethyl hydroxyethoxyethyl HEPT phosphonate (as well as its analogue from bromo HEPT), 2-chloroethyl hydroxypropoxypropyl MHEPT phosphonate.

In place of using tris (2-chloroethyl) phosphite as the starting material there can be used other tertiary phosphites of the formula (R,,O-) -,P where R is lower alkyl, lower. haloalkyl, lower alkenyl or lower haloalkenyl. The R, groups can be the same or different e.g. trimethyl phosphite, triethyl phosphite, triisopropyl phosphite, tributyl phosphite, tris (2-bromoethyl) phos- 60 phite, tris(2-fluoroethyl) phosphite, triallyl phosphite,

trimethyallyl phosphite, tris(2-chloroallyl) phosphite,

methyl diethyl phosphite, bis(2-chloropropyl) 2- chloroethyl phosphite.

Similar HEPT phosphonates can be formed by react- 5 ing hexachlorocylopentadiene with dialkyl lcyanovinyl phosphonates such as dimethyl l cyanovinyl phosphonate, diethyl l-cyanovinyl phosphonate, and dibutyl l-cyanovinyl phosphonate to form the corresponding dialkyl HEPT phosphonates. Reaction of these dialkyl HEPT phosphonates mole for By utilizing hexabromocyclopentadiene and alphabromoacrylonitrile there is formed l,2,4,5,6,7,7- heptabromo-2-cyano-5-norbornene (bromo HEPT) and by utilizing hexafluorocyclopentadiene and alpha fluoroacrylonitrile there is formed l,2,4,5,6,7,7- heptafluoro-Z-cyano-5-norbornene (fluoro HEPT). These compounds can be further reacted in the manner just described to form compounds such as ethyl hydroxyethoxy-ethyl bromo HEPT phosphonate, ethyl hydroxyethoxyethyl fluoro HEPT phosponate, 2- chloroethyl hydroxybutyl bromo HEPT phosphonate, 2-chloroethyl hydroxypropoxypropyl bromo HElPT phosphonate, 2-chloroethyl hydroxypropoxypropyl fluoro HEPT phosphonate, 3-bromopropyl hydroxyethoxyethyl fluoro HEPT phosphonate, Z-fluoroethyl.

hydropropoxypropyl bromo HEPT phosphonate, 2- fluoroethyl hydroxyethoxyethyl fluoro HEPT phosphonate, methyl hydroxypropoxypropyl bromo HEPT phosphonate, butyl hydroxyethoxypropyl fluoro HEPT phosponate, pentafluorophenyl hydroxyethoxyethyl fluoro HEPT phosphonate, trichlorophenyl hydroxypropoxypropyl bromo HEPT phosphonate.

Compounds analogous to 2-chloroethyl hydroxypropoxypropyl HEPT phosphonate are within the fori where X is Cl, Br or F (i.e. halogen of ammo weight up to X is Cl, Br, F, H, alkyl (e.g. methyl, ethyl, hexyl, hexadecyl, octadecyl, pentyl), alkoxy, haloalkyl,

32' haloalkoxy, R is alkyl, alkenyl, haloalkyl or haloalkenyl, e.g. methyl, ethyl, butyl, decyl, pentyl, hexyl, hexadecyl, octadecyl, allyl, 2-chloroethyl,.2-bromoethyl, 2-fluoroethyl, 2-chloroallyl, R is H(OR'), where R is lower alkylene of at least two carbon atoms, e.g. ethyl, propyl or butyl and n is an integer, e.g. 1,2,3 or 4. Any alkyl or alkenyl roup is preferably lower alkyl or alkenyl, e.g. up to four carbon atoms. Thus H(OR'),, can be Compounds of this type include methyl 2-hydroxyethyl HEPT phosphonate, allyl hydroxypropoxypropyl HEPT phosphonate, ethyl hydroxyethoxyethyl HEPT phosphonate, 3-chloropropyl hydroxyethoxyethyl 1,4,- 5,6,7,7-hexabromo-2-cyano-5-norbornene-2- phosphonate, 2-chloroethyl hydroxyethoxyethyl 1,4,5,- 6, 7,7-hexafluoro-2-cyano-5-norbornene-2- phosphonate, ethyl hydroxybutyl 1,4,5 ,6-tetrachl0ro-2- cyano-S-norbomene -2-phosphonate, 2-chloroethyl hydroxydipropoxypropyl l,4,5,6-tetrafluoro-2-cyano- 5-norbornene-2-phosphonate, 2-chloroallyl hydroxypropoxypropyl 1,4,5 ,6,7,7-hexachloro-2-cyano-5- norbornene-2-phosphonate, ,2-bromopropyl hydroxypropyl l,4,5,6-tetrachloro-7-ethoxy-2-cyano-5 -norbornene-2-phosphonate, Z-chloroethyl hydroxytriethoxyethyl l,4,5,6-tetrabromo-7-ethyh2-cyano-5- norbornene-2-phosphonate, allyl hydroxypropoxypropyl l,4,5,6-tetrachloro-7,7-dimethyl-2-cyano-5- norbornene-2'phosphonate, l,4,5,6,7-pentachloro-2- cyano-2-ethoxy-5-norbornene-7-phosphonate, chloroethyl hydroxyethoxyethyl l,4,5,6-tetrachloro- 7,7-dimethoxy-2-cyano-5-norbornene-2-phosphonate, 2,-chloroethyl hydroxyethoxyethyl l,4,5,6,7- pentachloro-7-chloroethyl-2-cyano-5-norbornene-2- phosphonate.

The general reaction for preparing the starting materials is chloroacylonitrile, alpha-bromoacrylonitrile or alphafluoroacrylonitrile (CH ziCN).

The phosphite reacted with the Diels-Alder product has the formula where R and R are alkyl, preferably lower alkyl, or 5 chloro lower alkyl, bromo lower alkyl or fluoro lower alkyl and R is lower alkylene of at least two carbon atoms, e.g. two to four carbon atoms, and n is an integer such as 1,2,3, or 4. One of R and R, can be aryl or haloaryl, e.g. phenyl, chlorophenyl, pentafluorophenyl, 1O dibromophenyl, tolyl.

In place of the tertiary phosphites there can be reacted alkali metal salts of secondary phosphites of the formula where R is alkyl, e.'g. methyl, ethyl, isopropyl, butyl, pentyl, hexyl, cyclohexyl, decyl, hexadecyl, octadecyl, halogen, e.g. chlorine, bromine or fluorine and T is halogen, e.g. chlorine, bromine or fluorine. (These compounds are prepared by the Diels-Alder reaction of hexahalocyclopentadiene with a compound having the formula CH ==CHR They can then be reacted by heating with a tertiary phosphite having the formula (R O) P where R,, is as previously defined to give phosphonates having the formulae OR e which in turn are reacted with diols to give products of 5s (if Rt=ha1ogen) the formulae (l1 Ra=ha1ogen) where R is as previously defined. Examples of such compounds within the invention are methyl hydroxypropoxypropyl 1,4,5 ,6,7-pentachloro-3-methyl-5- norbornene-7-phosphonate, 2-chloroethyl hydroxyethoxyethyl 1,4,5,6,7-pentachloro-3-ethyl-5- norbornene-7-phosphonate, 2-bromoethyl 4- hydroxybutyl 1,4,5 ,6,7-pentabromo-3-hexadecy|-5 norbornene-7-phosphonate, 3-chloropropyl hydroxypropoxypropyl 1,4,5,6,7-pentafluoro-3-bromo-5- norbornene-7-phosphonate, decyl hydroxypropoxypropyl l,4,5,6,7-pentach1oro-3-cyclohexyl-5-norbornene- 7-phosphonate, 2-chloropropyl hydroxyethoxyethyl 1,- 4,5,6,7-pentachloro-3-chl0ro-5-norbornene-7- phosphonate.

Somewhat similar compounds are formed by reacting octachloronorbornadiene, octabromonorbornadiene or octafluoronorbornadiene with a tertiary phosphite (R O) -,P followed by transesterification with a diol HO(R'O),,H to give phosphonates of the formula (when T is Cl) Examples of such phosphonates are butyl 4- hydroxybutyl 1,2,3,4,5,6,7-heptachloronorbornadiene- 7-phosphonate, 2-chloroethyl hydroxyethoxyethyl 1,2,- 3,4,5,6,7-heptach1oronorbornadiene-7-phosphonate, 3-bromopropyl hydroxypropoxypropyl l,2,3,4,5,6,7- heptafluoronorbomadiene-7-phosphonate. Illustrative of the intermediates is dimethyl 1,2,3,4,5,6,7- heptachloronorbornadiene-7-phosphonate (also called l,2,3,4,5,6,7-heptachloro-7-dimethoxyph0sphono 2,5- norbornadiene).

As in the reaction with HEPT the initial alkyl or haloalkyl phosphonates of all the types described above are prepared by dissolving the halogenated norbornene (or norbornadiene) compound in xylene (or other inert solvent) and heating to reflux under nitrogen. The tertiary phosphite is added slowly dropwise and the R Cl formed is removed as a gas. The product is then distilled to recover the phosphonate, either as a higher boiling fraction or. by crystallization.

EXAMPLE 51 Dimethyl HEPT Phosphonate.

900.8 grams (2.5 moles) of HEPT and 1.2 liters of xylene were placed in a 3 necked flask at roomtemperature in a nitrogen atomosphere and heated with stir ring. 372.3 grams (3.0 moles, a 20% excess) of trimethyl phosphite in 0.5 liters of xylene were added dropwise while the temperature in the flask rose from 73C. to about C. in 2 hours and 40 minutes. The mixture was cooled overnight and then reheated to 130C. for about 5 hours. The xylene and other low boilers such as excess trimethyl phosphite were removed by distillation first at atmospheric pressure and then at the water pump. The residue was filtered hot through charcoal. The residue was a dark brown viscous liquid (about 1 liter) and was redissolved in about 300 ml. of hot xylene and 600 ml. of ether. The mixture was filtered over charcoal. The filtrate was still dark brown. The filtrate was concentrated to 1.2 liters and placed in a refrigerator at -17C. The product did not crystallize.

393.2 grams was removed from the refrigerator and heated in a vacuum. 41 grams of distillate was obtained at 43.572.5C. at about 23 mm. This was discarded. The residue was vacuum distilled and 1 12.7 grams collected at 10113l.5C. and 0.3 to 2.5 mm.

Two more portions of the product were removed from the refrigerator and distilled in the manner just indicated to give a total of 320.1 grams of distillate product.

The product was then redistilled in a vacuum. Four cuts totaling 121.5 grams were collected at about 0.17-0.36 mm. and 78-103.5C. A fifth and main cut of 1629 grams of yellow liquid mixed with white crystals was taken at about 0.2 to 0.45 mm. and 71101C.

The liquid in the main cut after several months was decanted and vacuum distilled at 0.1 to 0.135 mm. to give a clear, colorless liquid with a white crystalline precipitate. The liquid portion had a 8.1. of 100 to 102C. at 0.10 to 0.13 mm. and analyzed C 26.96%, H 1.98%, Cl 50.14%, N 3.66%, P 6.17%. The product was dimethyl HEPT phosphonate and was designated CPNB, empirical formula c,,,H,,c1,0,NP.

EXAMPLE 52 11 grams (0.03 mole) of octachloronorbornadiene -2, 5 (a very pale yellow liquid B.P. 95l00C. at 0.40 mm.) and 30 ml. xylene (solvent) were placed in a flask and there was added 4.1 grams (about 0.033 mole) of trimethyl phosphite while a nitrogen atmosphere was maintained. The mixture was heated to reflux while allowing the methyl chloride formed to escape. Refluxing was continued for about 5.5 hours. Then xylene and volatiles were removed at the water pump and the unreacted octachloronorbornadiene removed under vacuum about 0.5 to 0.7 mm. The residue was 3.4 grams of a dark solid containing dimethyl 1,2,3,4,5,6,7- heptachloro-2,5-norbornadiene-7-phosphonate.

Pentaerythritol alkylene oxide adducts react with 3 moles of a tris(haloalkyl) phosphite to form a hexa(- haloalkyl) mono hydroxy alkyl pentaery-thritol triphosphite. The equation is as follows using Pluracol PEP 450 (adduct of pentaerythritol with 4 moles of propylene oxide having a molecular weight of about Thus there can'be prepared hexa(2-chloroethyl) 2- hydroxypropyl pentaerythritol triphosphite, hexa(2- chloroethyl) hydroxycthyl pentaerythritol triphosphite, hexa(Z-chloroethyl) Z-hydroxybutyl pentaerythritol triphosphite, hexa(2,3-dichloropropyl) 2- hydroxypropyl pentaerythritol triphosphite, hexa(2- chloropropyl) 2-hydroxypropyl pentaerythritol triphosphite, hexa-(3-chloropropyl) 2-hydroxypropyl pentaerythritol triphosphite, hexa(2-chloroethyl) 3- hydroxypropyl pentaerythritol triphosphite, hexa(2- fluororethyl)2-hydroxypropyl pentaerythritol tri- EXAMPLE 53 100.0 grams (0.25 mole) of Pluracol PEP 450 and 202.1 grams (0.75 mole) of tris(2-chloroethyl) phosphite were mixed under a nitrogen atmosphere and heated up to C. for 5 hours at 20-50 mm. to distill out 55.0 grams of 2-chloroethanol. The residue was a clear, colorless viscous liquid weighing 230.6 grams and was primarily hexa-(2-chloroethyl) tripropylene hydroxypropyl pentaerythritol triphosphite with a small amount of the isomeric phosphonate.

EXAMPLE 53a The reaction was carried out as in Example 53 except that Pluracol PEP 450 was replaced by 0.25 mole of pentaerythritol. The product was hexa-(Z-chloroethyl) hydroxypropylpentaerythritol triphosphite, a nearly colorless, viscous liquid.

Maleic anhydride reacts with diols such as ethylene glycol, propylene glycol, 1,4-butylene glycol, 1,2- butylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol on a mole for mole basis to give half esters, e.g. 2-hydroxyethyl hydrogen maleate, 2- hydroxypropyl hydrogen maleate, Z-hydroxypropyl hydrogen maleate, 3-hydroxypropyl hydrogen maleate, diethylene glycol hydrogen maleate, dipropylene glycol hydrogen maleate. These products react mole for mole with halogen containing tertiary phosphite to form halogen containing, monohydroxy succinate esters. A typical equation for the reactions is 1 Typical starting phosphites are tris(2-chloroethyl) phosphite, tris(Z-chloropropyl) phosphite,

37 tris(2-bromoethyl)phosphite, tris(2-fluoroethyl) phosphite, tris(2,3-dichloropropyl) phosphite, tris(2,3- dibromoethyl) phosphite.

Examples of products of the invention are 2- hydroxyethyl 2-chloroetnyl di(2-chloroethyl) phosphonosuccinate (HCPS), 2-hydroxyethyl 2-bromoethyl di(2-bromoethyl) phosphonosuccinate, 2- hydroxyethyl 2,3-dichloropropyl) di(2,3-dichloropropyl) phosphonosuccinate, 2-2-fluoroethyl di(2-fluoroethyl) phosphonosuccinate, 2-hydroxypropyl 2-chloropropyl di(2-ch1oropropyl) phosphonosuccinate, diethylene glycol 2-chloroethyl di(2-chloroethyl) phosphonosuccinate, dipropylene glycol 2-bromoethyl di(2- bromoethyl) phosphonosuccinate, dipropylene glycol 3-bromopropyl di(3-bromopropyl) phosphonosuccinate, diethylene glycol 2,3-dichloropropyl di(2,3- dichloropropyl) phosphonosuccinate, dipropylene glycol 2,3-dif1uoropropyl di(2,3-difluoropropyl) phosphonosuccinate.

EXAMPLE 54 980.6 grams (10.0 moles) of maleic anhydride were dissolved in 620.7 grams (10.0 moles) of ethylene glycol and heated in a nitrogen atmosphere at.23 to 65C. for 1.25 hours. An exotherm took the temperature to 69C. The mixture was held at 60 to 72C. for 2 hours with the aid of an ice-water bath and was then allowed to cool to room temperature. The acid number was 125.5 (theory 350). The mixture was heated again at 75C. for three hours at which time the acid number had risen to 328. The mixture was heated an additional hour at 75C. to get an acid number of 334. Heating was continued for 3 more hours at 75C. The acid number was 314. The hydroxyl number was 745 (theory 745). The 2-hydroxyethyl hydrogen maleate was a clear yellow liquid and weighed 1,595.0 grams, C 45.84%, H 5.41%.

EXAMPLE 55 800.6 grams (5.0 moles) of 2-hydroxyethyl hydrogen maleate prepared in Example 54 was heated to 50C. under a nitrogen atmosphere. There was added dropwise 1,347.5 grams of tris(2-chloroethyl) phosphite in 2 hours at 5080C., the exotherm maintaining the temperature without external heating. Then the clear golden solution was heated at 100C. for 8 hours. The acid number was now 1.5. The bright orange clear liquid was 2-hydroxyethyl 2-chloroethy1di(2-chloroethyl) phosphonosuccinate in a yield of 2,100 grams, analyzing C 34.20%, H 5.16%, CI 24.62%, P 5.57%.

EXAMPLE 56 490.3 grams (5.0 moles) of maleic anhydride were mixed with 530.6 grams (5.0 moles) of diethylene glycol at 25C. in a nitrogen atmosphere. The temperature dropped to 19C. due to the endothermic reaction. Heating was begun to speed up the dissolution of the maleic anhydride. Complete dissolution occurred at 48C. The temperature was then held at 60-80C. for 1 hour and then kept at 75C. for 3 hours at which time the acid number was 286.1. The product was heated further at 75C. for an additional 2.5 hours. The hydroxyethoxyethyl hydrogen maleate formed was a clear, golden yellowish orange liquid, acid number 272.2 (theory 274.8), and weighed 1,012.4 grams, hy-

droxyl number 546 (theory 609.5), C 46.82%, H 6.11%.

EXAMPLE 57 510.5 grams (2.5 moles) of hydroxyethoxyethyl hydrogen maleate prepared in Example 56 were placed under a nitrogen atmosphere. Then there were added dropwise 673.7 grams (2.5 moles) of tris(2- chloroethyl) phosphite at 5080C. in 1.5 hours. The solution was heated to 100C. for 2 hours at which time the acid number was 14.93. Heating was continued for 4.5 hours more at 100C. to an acid number of 2.6 (theory is zero); The 2-hydroxyethoxyethyl 2-chloroethyl di(2-chloroethyl) phosphonosuccinate formed was a clear, viscous, pale orange liquid weighing 1,170.1 grams, C 35.31%, H 5.10%, Cl 22.42%, P 6.02%.

EXAMPLE 5 8 490.3 grams (5.0 moles) of maleic anhydride were mixed with 670.9 grams (5.0 moles) of dipropylene glycol at C. in a nitrogen atmosphere. The temperature dropped to 20C. during 15 minutes of stirring. The mixture was heated to C. and held there for 2 hours. The acid number was 271.7 (theory 241.6). Heating was continued for 4.5 hours more at 75C. to get an acid number of 247.2. The 2-hydroxypropoxypropyl hydrogen maleate obtained was a clear, viscous, pale orange liquid weighing 1,146.3 grams, hydroxyl number 428.8 (theory 545), C 51.52%, H 6.78%.

EXAMPLE 59 580.6 grams (2.5 moles) of 2-hydroxypropoxypropy1 hydrogen maleate prepared in Example58 were placed under a nitrogen atmosphere and 673.7 grams (2.5 moles) of tris(2-chloroethyl) phosphite added drop wise at 50-70C. in 1.5 hours. The mixture was then heated at C. for 1 hour to an acid number of 14.48. The mixture was then heated for 4 more hours at 100C. to an acid number of 5.56. The 2-hydroxypropoxypropyl 2-ch1oroethyl di(2-chloroethyl) phosphonosuccinate was a clear, golden yellow, viscous liquid weighing 1,240.1 grams, hydroxyl number 128.3 (theory 111.8), C 38.87%, H 5.97%, Cl 21.22%, P 5.07%. i

An alternative method of preparation of bis( 2- chloroethyl)hydroxypropoxypropyl phosphite, the product of Examples 3, 8, 14, 2 0 and 28 is given below. Similar compounds are prepared in an analogous manner, where R and R each is alkylene, alkenylene, or substituted alkylene, e.g.,

#0115011? or orig-01k,

and X is Cl, Br or F in the following equation 2 (XRO--) P (HOR'OR'O-hP m? 3 (XRO- P-OR'OR 'OH The heating to obtain the above exhange of ester groups is carried but usually at 80' l30C. in order to complete this reaction but to minimize the rearrangement to the corresponding phosphonate. 1f the heating is continued for several hours in the'range of to 7 200C., the following rearrangement takes place (grad- 

2. A compound according to claim 1 having formula (a).
 3. A compound according to claim 2 wherein R1 and R2 are haloalkyl of one to eight carbon atoms.
 4. A compound according to claim 3 wherein R1 and R2 are haloalkyl of two to three carbon atoms, and R3 is alkylene of two to three carbon atoms, there are one to two halogen atoms on each alkyl group and n is an integer not over
 3. 5. A compound according to claim 4 which is bis(2-chloroethyl) hydroxyethoxyethyl phosphite.
 6. A compound according to claim 4 which is bis(2-chloroethyl) hydroxypropoxypropyl phosphite.
 7. A compound according to claim 4 which is bis(2,3-dichloropropyl) hydroxypropoxypropyl phosphite.
 8. A compound according to claim 3 which is bis(2-chloroethyl) 2-hydroxy-3-chloropropyl phosphite.
 9. A compound according to claim 4 which is bis(2,3-dichloropropyl) hydroxyethoxyethyl phosphite.
 10. A compound according to claim 4 which is bis(2-chloropropyl) hydroxyethoxyethyl phosphite.
 11. A compound according to claim 1 having formula (b).
 12. A compound according to claim 11 wherein R1 and R2 are haloalkyl of one to eight carbon atoms.
 13. A compound according to claim 12 wherein R1 is haloalkyl of two to three carbon atoms, R2 is haloalkyl of one to three carbon atoms and R3 is alkylene of two to three carbon atoms, there are one to two halogen atoms on R1 and one to three halogen atoms on R2 and n is an integer not over
 3. 14. A compound according to claim 13 which is 2-chloroethyl hydroxyethoxyethyl trichloromethane phosphonate.
 15. A compound according to claim 13 which is 2-chloroethyl hydroxyethoxyethyl 2-chloroethane phosphonate.
 16. A compound according to claim 13 which is 2-chloroethyl hydroxpropoxypropyl trichloromethane phosphonate.
 17. A compound according to claim 13 which is 2-chloroethyl hydroxypropoxypropyl 2-chloroethane phosphonate.
 18. A compound according to claim 13 which is 2,3-dichloropropyl hydroxypropoxypropyl 2,3-dichloropropane phosphonate.
 19. A compound according to claim 13 which is 2-chloropropyl hydroxyethoxyethyl 2-chloropropane phosphonate.
 20. A compound according to claim 13 which is 2-chloropropyl hydroxyethoxyethyl trichloromethane phosphonate.
 21. A compound according to claim 13 which is 2-chloropropyl hydroxypropoxypropyl trichloromethane phosphonate.
 22. A compound according to claim 1 wherein the halo lower alkyl group has one to eight carbon atoms and the halo lower alkenyl group is haloallyl.
 23. A compound according to claim 22 wherein at least one of R1 and R2 is halocycloalkenyl.
 24. A compound according to claim 23 wherein the halocycloalkenyl is a polyhalobiCycloalkenyl group.
 25. A compound according to claim 24 wherein the halocycloalkenyl is halo-norbornenyl.
 26. A compound having one of the formulae:
 27. A compound according to claim 26 having formula (a).
 28. A compound according to claim 27 wherein R6 is halo lower alkyl.
 29. A compound according to claim 28 wherein R5 includes a polyhalocyclohexenyl group.
 30. A compound according to claim 29 wherein R3 has 2 to 3 carbon atoms and n is
 2. 31. A compound according to claim 30 wherein R5 is 1,4,5,6,7,7-hexachloro-5-norbornen-2-yl.
 32. A compound according to claim 26 having formula (b).
 33. A compound according to claim 32 wherein R7 is halo lower alkyl.
 34. A compound according to claim 33 wherein R5 includes a polyhalocyclohexenyl group.
 35. A compound according to claim 34 wherein R3 has two to three carbon atoms and n is
 2. 36. A compound according to claim 35 wherein R5 is 1,4,5,6,7,7-hexachloro-5-norbornen-2-yl. 